Process for preparing alkyl-subtituted aromatic hydrocarbons

ABSTRACT

An alkyl-substituted hydrocarbon is prepared by alkylating an aromatic hydrocarbon having at least one hydrogen atom at an alpha-position in a side chain with an olefin in the presence of a solid base which is obtainable by heating an alumina, an alkali metal hydroxide and an alkali metal or an alumina containing at least 1.3% by weight of water and an alkali metal in an inert gas atmosphere at a specific temperature as a catalyst.

CROSS-REFERENCE TO THE RELATED APPLICATION

This application is a continuation of application Ser. No. 07/570,548which is a continuation-in-part of application Ser. No. 305,755 filed onFeb. 3, 1989, now both abandoned.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to a process for preparing analkyl-substituted aromatic hydrocarbon. More particularly, the presentinvention relates to a process for preparing an alkyl-substitutedaromatic hydrocarbon by reacting an alkyl-substituted aromatichydrocarbon having at least one hydrogen atom at an alpha-position insaid alkyl side chain with an olefin in the presence of a solid basewhich is prepared from an alumina, an alkali metal hydroxide and analkali metal or from water-containing alumina and an alkali metal at atemperature in a specific range, whereby the alpha position isalkylated.

The alkyl-substituted aromatic hydrocarbons are useful as intermediatesin the production of fine chemicals such as agricultural chemicals,medicines and other chemicals and prepared by reacting the aromatichydrocarbon having the hydrogen atom at the alpha-position in the sidechain with the olefin in the presence of a base catalyst.

As the preparation process of the alkyl-substituted aromatichydrocarbon, there are known a process which utilizes a catalystcomprising metal sodium and chlorotoluene and a process which utilizes acatalyst comprising metal sodium supported on potassium carbonate (cf.J. Am. Chem. Soc., 78, 4316 (1956), GB Patent No. 1269280 and JapanesePatent Kokai Publication No. 53229/1986).

However, the conventionally used catalysts have various drawbacks suchas insufficient catalytic activities, a low yield of thealkyl-substituted hydrocarbon per a unit amount of the catalyst andtroublesome separation of the catalysts from the product. Further, theconventional catalysts suffer from such problem that when they contactthe oxygen and/or moisture in the air, they tend to lose theiractivities or they are ignited.

SUMMARY OF THE INVENTION

One object of the present invention is to provide a base catalyst whicheffectively catalyzes the reaction of the aromatic hydrocarbon havingthe hydrogen atom at the alpha-position in the side chain with theolefin, can be easily separated from the product after reaction.

Another object of the present invention is to provide a process forproducing an alkyl-substituted hydrocarbon by reacting the aromatichydrocarbon having the hydrogen atom at the alpha-position in the sidechain with the olefin.

Accordingly, the present invention provides a process for preparing analkyl-substituted hydrocarbon comprising alkylating an aromatichydrocarbon having a hydrogen atom at a alpha-position in a side chainwith an olefin in the presence of a solid base which is obtainable byheating an alumina, an alkali metal hydroxide and an alkali metal or analumina containing at least 1.3% by weight of water and an alkali metalin an inert gas atmosphere at a temperature of 200° to 600° C. as acatalyst.

DETAILED DESCRIPTION OF THE INVENTION

The process of the present invention is characterized in the use of thespecific solid base as the catalyst, which solid base is prepared byheating the alumina, the alkali metal hydroxide and the alkali metal atthe specific temperature.

As the alumina, various types of aluminas except α-alumina are used.Preferred examples of the alumina are γ-alumina, χ-alumina andρ-alumina. Among them, those having a relatively large surface area arepreferred.

As the alkali metal, an alkali metal of Group I of the Periodic Tablesuch as lithium, sodium, potassium and rubidium is used. They may beused as a mixture or an alloy. Among them, sodium, potassium and analloy of them, particularly potassium are preferred. The amount of thealkali metal is generally from 2 to 15% by weight based on the weight ofthe alumina.

As the alkali metal hydroxide, any of hydroxides of the aboveexemplified alkali metals may be used. Preferably, sodium hydroxide,potassium hydroxide and cecium hydroxide are used. Mixtures of two ormore alkali metal hydroxides may be used. The amount of the alkali metalhydroxide is generally from 5 to 40% by weight based on the weight ofthe alumina.

In the preparation of the solid base, preferably the alumina is treatedwith the alkali metal hydroxide, and then the resulting product isreacted with the alkali metal in the inert gas atmosphere.

For example, the alumina is heated to a desired temperature and mixedwith the alkali metal hydroxide while stirring. Thereafter, the alkalimetal is added to the resulting product and heating of the resultingmixture is continued while stirring. Alternatively, the alkali metalhydroxide can be used in the form of an aqueous solution, provided thatwater in such solution is sufficiently removed prior to the addition ofthe alkali metal. Thereafter, the alkali metal is added to the driedproduct and further heated.

As the inert gas, nitrogen, helium, argon and the like are used.

In the preparation of the solid base to be used in the process of thepresent invention, the reaction temperature is important. Usually, thereaction temperature is from 200° to 600° C. Preferably, the alumina andthe alkali metal hydroxide are reacted in a temperature range of 250° to550° C., more preferably in a temperature range of 260° to 480° C., andthe alkali metal is reacted in a temperature range of 200° to 450° C.

Moreover, in the case of the solid base which is prepared by usingsodium as an alkali metal and potassium hydroxide as an alkali metalhydroxide, the alumina and potassium hydroxide are reacted in atemperature range of 200° to 390° C., more preferably in a temperaturerange of 270° to 390° C.

The reaction time varies with other reaction conditions such as thereaction temperature. The reaction of the alumina with the alkali metalhydroxide may be completed within 0.5 to 10 hours, and the treatmentwith the alkali metal may be completed within 10 to 300 minutes.

By the above reactions, the solid base which has high catalyticactivity, good flowability and handleability can be obtained.

When water-containing alumina containing at least 1.3% by weight ofwater is used as the alumina, the solid base having the same catalyticperformances as above can be prepared with using no alkali metalhydroxide. Namely, the solid base catalyst can be prepared by reactingthe alumina containing at least 1.3% by weight of water with the alkalimetal in the inert gas atmosphere at a temperature of 200° to 600° C.

Various types of water-containing aluminas except for α-alumina can beused.

Generally, alumina is produced by calcining aluminum hydroxide.According to the calcining temperature and time, alumina has variousmetastable states and a water content varies so that various type ofalumina are produced. In the present invention, such alumina may beused. Preferably, water-containing alumina with a large surface areasuch as γ-alumina, χ-alumina, ρ-alumina and η-alumina are used.

The water content may be expressed by weight loss on heating in theheating step in which the alumina in its original state is converted toα-alumina which is considered to include no removable water. Usually,the water content of the water-containing alumina is 1.3 to 15% byweight, preferably 2 to 10% by weight.

The amount of alkali metal used in this preparation method is generallyfrom 1.01 to 2 time molar equivalents of water contained in the alumina.

Again, the reaction temperature is important in this preparation methodof the catalyst. Usually, the reaction temperature is from 200° to 600°C., preferably from 250° to 550° C., more preferably from 260° to 480°C.

The reaction time varies with other reaction conditions such as thereaction temperature. The reaction of the alumina and the alkali metalmay be completed within 10 to 300 minutes.

By the above reaction, the solid base which has the same properties asthat prepared from the alumina, the alkali metal hydroxide and thealkali metal, such as high catalytic activity, good flowability andhandleability can be obtained. This may be because a part of the alkalimetal reacts with the water contained in the alumina to form thecorresponding alkali metal hydroxide and as the result, the alumina, thealkali metal hydroxide and the alkali metal react with each other.

In the process of the present invention, the aromatic hydrocarbon havingthe hydrogen atom at the alpha-position in the side chain is reactedwith the olefin in the presence of the above described solid base as thecatalyst.

As such aromatic hydrocarbon, not only monocyclic aromatic hydrocarbonsbut also condensed polycyclic aromatic hydrocarbons may be used. In thearomatic hydrocarbons, the side chains may be closed to form a ring.Specific examples of the aromatic hydrocarbon are toluene, ethylbenzene,isopropylbenzene (cumene), n-propylbenzene, n-butylbenzene,sec.-butylbenzene, isobutylbenzene, xylene, cymene, diisopropylbenzene,methylnaphthalene, tetrahydronaphthalene, indan and the like. Amongthem, toluene, ethylbenzene and isopropylbenzene are preferred.

As the olefin, those having 2 to 20 carbon atoms are usually used. Theolefin may be straight or branched. The carbon-carbon double bond may bea terminal or internal double bond. Preferably, the olefin having theterminal double bond is used. Specific examples of the olefin areethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene,2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene,3-heptene, octene, nonene, 3-methyl-1-butene, 2-methyl-2-butene,3-methyl-1-pentene, 3-methyl-2-pentene and the like. Among them,ethylene, propylene, 1-butene and 2-butene are preferred.

The alkylation reaction according to the present invention may becarried out batchwise or continuously with the use of a fluidized bed ora fix bed.

The reaction temperature for the alkylation is usually from 0° to 300°C., preferably from 20° to 200° C.

The reaction pressure is from atmospheric pressure to 200 kg/cm²,preferably from 2 to 100 kg/cm².

The molar ratio of the olefin to the aromatic hydrocarbon is usuallyfrom 0.1 to 10, preferably from 0.2 to 5.

In the batchwise reaction, the amount of solid base catalyst to be usedis from 0.1 to 20% by weight, preferably from 0.2 to 5% by weight basedon the weight of the aromatic hydrocarbon. The reaction time isgenerally from 0.5 to 50 hours, preferably from 1 to 25 hours.

In the continuous reaction, the mixture of the aromatic hydrocarbon andthe olefin in the above molar ratio is supplied at LHSV of 0.1 to 600hr⁻¹, preferably 0.5 to 400 hr⁻¹.

According to the present invention, the alkyl-substituted hydrocarbon iseffectively prepared in the presence of the solid base catalyst in asmall amount under the mild conditions. Further, the catalyst to be usedaccording to the present invention is easily handled and post-treatedafter the reaction.

PREFERRED EMBODIMENTS OF THE INVENTION

Practically and presently preferred embodiments of the present inventionwill be illustrated by following examples.

Preparation of Solid Bases

Solid Base A

42-200 Mesh activated alumina (NKHD-24, a trade name of SumitomoChemical Co., Ltd.) (26.5 g) was stirred in an atmosphere of nitrogen at500° C. for 2 hours and cooled to 350° C. Then, potassium hydroxide (2.5g) was added to the alumina and the mixture was stirred at 350° C. for 3hours followed by cooling to 290° C.

To the mixture, metal potassium (2.0 g) was added and the mixture wasstirred at 290° C. for 0.5 hour followed by cooling to room temperatureto obtain Solid Base A (24 g).

Solid Base B

In the same manner as in the preparation of Solid Base A but addingpotassium hydroxide at 250° C. and stirring the mixture of the aluminaand potassium hydroxide at 250° C., Solid Base B was prepared.

Solid Base C

In the same manner as in the preparation of Solid Base A but addingpotassium hydroxide at 480° C. and stirring the mixture of the aluminaand potassium hydroxide at 480° C., Solid Base C was prepared.

Solid Base D

In the same manner as in the preparation of Solid Base A but stirringthe activated alumina at 580° C. for 1 hour, adding potassium hydroxideat 580° C. and stirring the mixture of the alumina and potassiumhydroxide at 580° C., Solid Base D (24.1 g) was prepared.

Solid Base E

In the same manner as in the preparation of Solid Base A but usingsodium hydroxide (2.5 g) in place of potassium hydroxide, Solid Base E(24.1 g) was prepared.

Solid Base F

In the same manner as in the preparation of Solid Base A but usingsodium hydroxide (2.5 g) in place of potassium hydroxide and using metalsodium (2.0 g) in place of metal potassium, Solid Base F was prepared.

Solid Base G

Activated alumina having the average central particle size of 80 μm(BK-570, a trade name of Sumitomo Chemical Co., Ltd.) (50 g) was stirredin an atmosphere of nitrogen at 500° C. for 1 hour and cooled to 350° C.Then, potassium hydroxide (5.65 g) was added to the alumina and themixture was stirred at 350° C. for 3 hours followed by cooling to 290°C. To the cooled mixture, metal potassium (4.06 g) was added and theresulting mixture was stirred at 290° C. for 0.2 hour followed bycooling to room temperature to obtain Solid Base G (55.2 g).

Solid Base H

In the same manner as in the preparation of Solid Base G but using 4.02g of metal potassium, adding metal potassium at 350° C. and stirring theresulting mixture at 350° C., Solid Base H was prepared.

Solid Base I

In the same manner as in the preparation of Solid Base G but using 4.15g of metal potassium, adding metal potassium at 220° C. and stirring theresulting mixture at 220° C., Solid Base I was prepared.

Solid Base J

In the same manner as in the preparation of Solid Base G but using 50 gof 48-200 mesh activated alumina (NKH 3-24), 4.73 g of potassiumhydroxide and 2.29 g of metal potassium, Solid Base J was prepared.

Solid Base K

The same activated alumina as used in the preparation of Solid Base A(26.5 g) and potassium hydroxide (2.5 g) were ground and mixed and thenplaced in a crucible and heated at 1,200° C. for 3 hours in a mufflefurnace. The mixture was cooled to 200° C. and further to roomtemperature in a desiccator in an atmosphere of nitrogen to obtain afine powder.

The fine powder was heated to 290° C. Then, to the heated powder, metalpotassium (2.0 g) was added while stirring. The mixture was furtherstirred at 290° C. for 0.5 hour followed by cooling to room temperatureto obtain Solid Base K.

Solid Base L

In the same manner as in the preparation of Solid Base K but using 2.0 gof metal sodium in place of metal potassium, Solid Base L was prepared.

Solid Base M

In the same manner as in the preparation of Solid Base K but heating themixture of the activated alumina and potassium hydroxide at 900° C. inthe muffle furnace, Solid Base M was prepared.

EXAMPLE 1

In a 600 ml autoclave equipped with a magnetic stirrer, Solid Base A(0.39 g) and cumene (240 g) were charged under nitrogen, heated to 105°C. while stirring and then reacted at the same temperature for 1.5 hourswhile supplying ethylene gas under pressure of 10 kg/cm² G. to producetert.-amylbenzene (hereinafter referred to as "TAB").

After the reaction, the autoclave was cooled, and the catalyst wasfiltered off. The reaction mixture was analyzed with gas chromatography.The results are shown in Table 1.

The selectivity of TAB is calculated according to the followingequation: ##EQU1##

                  TABLE 1                                                         ______________________________________                                        Exam-  Solid  Reaction Reaction                                                                             Conversion                                                                            Selectivity                             ple    Base   Temp.    Time   of cumene                                                                             of TAB                                  No.    (g)    (°C.)                                                                           (hrs)  (%)     (%)                                     ______________________________________                                        1      0.39   105      1.5    85.5    99.4                                    2      0.37   160      3      99.8    99.3                                    3      0.38    42      1.5    46.9    99.6                                    ______________________________________                                    

EXAMPLES 2-3

In the same manner as in Example 1 but carrying out the reaction underthe conditions shown in Table 1, the alkylation was carried out. Theresults are shown in Table 1.

EXAMPLES 4-9 AND COMPARATIVE EXAMPLES 1-2

In the same manner as in Example 1 but using one of Solid Bases A to F,K and L and 160 g of cumene and carrying out the reaction at 160° C.,the alkylation was carried out. The results are shown in Table 2.

In Examples 1-9, the catalyst was still active at the end of thereaction and the alkylation could be further carried out by using thesame catalyst.

                  TABLE 2                                                         ______________________________________                                        Example Solid Base   Conversion  Selectivity                                  No.     Kind    grams    of Cumene (%)                                                                           of TAB (%)                                 ______________________________________                                        4       A       0.44     94.9      99.5                                       5       B       0.74     87.6      99.3                                       6       C       0.43     92.9      97.9                                       7       D       0.45     40.4      88.9                                       8       E       0.43     76.3      98.9                                       9       F       0.90     61.1      99.7                                       Comp. 1 K       0.88     20.2      70.7                                       Comp. 2 L       0.98     7.5       98.4                                       ______________________________________                                    

EXAMPLE 10

In a 230 ml autoclave equipped with a magnetic stirrer, Solid Base G(0.85 g) and cumene (88 g) were charged under nitrogen, heated to 162°C. while stirring and then reacted at the same temperature for 6.5 hourswhile supplying ethylene gas under pressure of 30 kg/cm² G to produceTAB. After the reaction, the product was analyzed in the same manner asin Example 1 to find that the conversion of cumene was 88% and theselectivity of TAB was 100%.

EXAMPLE 11

In a 300 ml autoclave equipped with a magnetic stirrer, Solid Base A(0.86 g) and cumene (80 g) were charged under nitrogen and then liquidpropylene (120 ml) was injected under pressure. The reaction was thencarried out at 160° C. for 36 hours while stirring to produce1,1,2-trimethylpropylbenzene (hereinafter referred to as "TMPB").

After the reaction, the autoclave was cooled, and the reaction mixturewas analyzed in the same manner as in Example 1. The results are shownin Table 3.

The selectivity of TMPB is calculated according to the followingequation: ##EQU2##

EXAMPLES 12-15

In the same manner as in Example 11 but using one of Solid Bases G to Jin place of Solid Base A and an 230 ml autoclave in Example 12 andcarrying out the reaction under the conditions shown in Table 3, thealkylation was carried out. The results are shown in Table 3.

In Examples 11-15, the catalyst was still active at the end of thereaction and the alkylation could be further carried out by using thesame catalyst.

                                      TABLE 3                                     __________________________________________________________________________                                  Conversion                                                                          Selectivity                               Example                                                                            Solid Base                                                                           Cumene                                                                             Propylene                                                                           Temp.                                                                             Time                                                                             of cumene                                                                           of TMPB                                   No.  Kind                                                                             grams                                                                             (g)  (ml)  (°C.)                                                                      (hrs)                                                                            (%)   (%)                                       __________________________________________________________________________    11   A  0.86                                                                              80   120   160 36 77.8  86.0                                      12   G  1.92                                                                              88   94    162 21 69.0  87.2                                      13   H  1.62                                                                              79.5 90    160 24 78.1  88.0                                      14   I  1.66                                                                              79   85    160 24 56.2  89.5                                      15   J  1.19                                                                              80   80    160 24 48.4  88.0                                      __________________________________________________________________________

COMPARATIVE EXAMPLE 3

In a 200 ml autoclave equipped with a magnetic stirrer, anhydrouspotassium carbonate which had been calcined at 400° C. for 2 hours in anitrogen atmosphere (8.86 g), metal sodium 0.30 g) and cumene (81.2 g)were charged under nitrogen, heated to 190° C. and then stirred at thesame temperature for 2 hours.

After cooling the autoclave, liquid propylene (70 ml) was injected underpressure and the mixture was stirred at 160° C. for 24 hours.

After the reaction, the product was analyzed in the same manner as inExample 1 to find that the conversion of cumene was 8.0% and theselectivity of TMPB was 81.5%.

EXAMPLE 16

In a 300 ml autoclave equipped with a magnetic stirrer, Solid Base A(4.07 g) and toluene (79.5 g) were charged under nitrogen and thenliquid propylene (70 ml) was injected under pressure. The mixture wasstirred at 163° C. for 6 hours to obtain isobutylbenzene (hereinafterreferred to as "IBB").

After the reaction, the product was analyzed in the same manner as inExample 1. The results are shown in Table 4. The selectivity of IBB iscalculated according to the following equation: ##EQU3##

EXAMPLES 17-20 AND COMPARATIVE EXAMPLE 4

In the same manner as in Example 16 but using one of Solid Bases B to D,J and M in place of Solid Base A, the reaction was carried out. Theresults are shown in Table 4.

In Examples 16-20, the catalyst was still active at the end of thereaction and the alkylation could be further carried out by using thesame catalyst.

                  TABLE 4                                                         ______________________________________                                        Example Solid Base   Conversion of                                                                              Selectivity                                 No.     Kind    grams    Toluene (%)                                                                              of IBB (%)                                ______________________________________                                        16      A       4.07     36.3       91.8                                      17      B       4.19     26.6       90.7                                      18      C       3.45     28.2       91.5                                      19      D       3.29     17.8       93.6                                      20      J       3.61     29.8       92.0                                      Comp. 4 M       3.37     8.6        85.0                                      ______________________________________                                    

COMPARATIVE EXAMPLE 5

In a 200 ml autoclave equipped with a magnetic stirrer having a nitrogeninterior atmosphere, anhydrous potassium carbonate which had beencalcined at 400° C. for 2 hours in a nitrogen atmosphere (8.45 g), metalsodium 0.30 g) and toluene (26.6 g) were charged and then stirred at190° C. for 2 hours.

After cooling the autoclave, additional toluene (53.2 g) was added andliquid propylene (70 ml) was injected under pressure. Then the mixturewas stirred at 160° C. for 6 hours.

After the reaction, the product was analyzed in the same manner as inExample 1 to find that the conversion of toluene was 3.5% and theselectivity of IBB was 88.2%.

EXAMPLE 21

In a 200 ml autoclave equipped with a magnetic stirrer, Solid Base J(0.7 g) and toluene (81 g) were charged under nitrogen, heated to 160°C. and then reacted at the same temperature for 6 hours while supplyingethylene gas under pressure of 10 kg/cm² G.

After the reaction, the product was analyzed in the same manner as inExample 1 to find that the conversion of toluene was 28.2%, theselectivity of n-pryopylbenzene was 78.6% and the selectivity of1-ethylpropylbenzene was 20.9%.

Preparation of Solid Bases

Solid Base N

To 40-200 mesh activated alumina containing 3.6% of water (21.7 g)heated at 290° C. in an atmosphere of nitrogen, metal potassium (2.08 g)was added while stirring and the mixture was further stirred at the sametemperature for 0.2 hour followed by cooling to room temperature toobtain Solid Base N (23.2 g).

Solid Base O

In the same manner as in the preparation of Solid Base N but using 2.5 gof metal potassium, changing the temperature to 350° C. and heating themixture of the alumina and metal potassium for 0.4 hour while stirring,Solid Base O was prepared.

Solid Base P

In the same manner as in the preparation of Solid Base N but changingthe temperature to 150° C., Solid Base P was prepared.

Solid Base Q

To 40-200 mesh activated alumina containing 1.0% of water (21.8 g)heated at 290° C. in an atmosphere of nitrogen, metal potassium (2.0 g)was added while stirring and the mixture was further stirred at the sametemperature for 0.2 hour followed by cooling to room temperature toobtain Solid Base Q.

Solid Base R

To the same water-containing alumina as used in the preparation of SolidBase N (21.7 g) heated at 290° C. in an atmosphere of nitrogen, metalpotassium (0.88 g) was added while stirring and the mixture was furtherstirred at the same temperature for 1 hour.

Then, the mixture was poured in a crucible and heated at 1,200° C. for 3hours in a muffle furnace. The mixture was cooled to 200° C. and furtherto room temperature in a desiccator in an atmosphere of nitrogen.

After heating the mixture to 290° C. in an atmosphere of nitrogen, metalpotassium (1.2 g) was added and the mixture was stirred at 290° C. for0.2 hour followed by cooling to room temperature to obtain Solid Base R.

Solid Base S

To activated alumina containing 1.1% by weight of water and having theaverage central particle size of 80 μm (18.9 g), metal potassium (1.59g) was added at 290° C. while stirring in an atmosphere of nitrogen andthe mixture was further stirred at the same temperature for 0.2 hourfollowed by cooling to room temperature to obtain Solid Base S.

EXAMPLE 22

In a 600 ml autoclave equipped with a magnetic stirrer, Solid Base N(0.45 g) and cumene (240 g) were charged under nitrogen, heated to 160°C. while stirring at 1,000 rpm and then reacted at the same temperaturefor 2 hours while supplying ethylene gas under pressure of 10 kg/cm² G.to produce TAB.

After the reaction, the autoclave was cooled, and the product wasanalyzed with gas chromatography. The results are shown in Table 5.

EXAMPLE 23 AND COMPARATIVE EXAMPLES 6-7

In the same manner as in Example 22 but using one of Solid Bases O, Qand R in place of Solid Base N, the alkylation was carried out. Theresults are shown in Table 5.

In Examples 22 and 23, the catalyst was still active at the end of thereaction and the alkylation could be further carried out by using thesame catalyst.

COMPARATIVE EXAMPLE 8

In a 200 ml autoclave equipped with a magnetic stirrer, anhydrouspotassium carbonate which had been calcined at 400° C. for 2 hours in anitrogen atmosphere (8.19 g), metal sodium (0.30 g) and cumene (26.7 g)were charged under nitrogen, heated to 190° C. and then stirred at 1,000rpm at the same temperature for 2 hours.

After cooling the autoclave, cumene (53.3 g) was further added, and themixture was heated to 160° C. while stirring at 1,000 rpm and thereacted while supplying ethylene gas under pressure of 10 kg/cm² G for 3hours. The results are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                        Example Solid Base   Conversion  Selectivity                                  No.     Kind    grams    of Cumene (%)                                                                           of TAB (%)                                 ______________________________________                                        22      N       0.44     99.6      97.8                                       23      O       0.45     88.9      97.4                                       Comp. 6 Q       1.50     24.0      61.4                                       Comp. 7 R       1.62     30.6      65.0                                       Comp. 8 Mixture 8.49 19.4        73.9                                         ______________________________________                                    

EXAMPLE 24

In a 300 ml autoclave equipped with a magnetic stirrer having a nitrogeninterior atmosphere, Solid Base N (1.07 g) and cumene (80 g) werecharged and then liquid propylene (100 ml) was injected under pressure.The reaction was carried out at 160° C. for 24 hours.

After the reaction, the catalyst was filtered off and the reactionproduct was analyzed with gas chromatography. The results are shown inTable 6.

The catalyst was still active at the end of the reaction and thealkylation could be further carried out by using the same catalyst.

COMPARATIVE EXAMPLE 9

In the same manner as in Example 24 but using Solid Base S in place ofSolid Base N, the alkylation was carried out. The results are shown inTable 6.

                  TABLE 6                                                         ______________________________________                                                                                Selec-                                Exam-            Propyl-        Conversion                                                                            tivity                                ple   Solid Base lene     Time  of Cumene                                                                             of TMPB                               No.   Kind   grams   (ml)   (hrs) (%)     (%)                                 ______________________________________                                        24    N      1.07    100    24    69.2    86.6                                Comp. S      1.16     60    20    5.0     86.0                                 9                                                                            ______________________________________                                    

EXAMPLE 25

In a 300 ml autoclave equipped with a magnetic stirrer having a nitrogeninterior atmosphere, Solid Base N (3.6 g) and toluene (79.5 g) werecharged and then liquid propylene (70 ml) was injected under pressure.The mixture was thereafter stirred at 163° C. for 6 hours.

After the reaction, the product was analyzed with gas chromatography.The results are shown in Table 7.

EXAMPLE 26 AND COMPARATIVE EXAMPLES 10-11

In the same manner as in Example 25 but using one of Solid Bases O, Pand S in place of Solid Base N, the alkylation was carried out. Theresults are shown in Table 7.

In Examples 25 and 26, the catalyst was still active at the end of thereaction and the alkylation could be further carried out by using thesame catalyst.

    ______________________________________                                        Example Solid Base   Conversion of                                                                              Selectivity                                 No.     Kind    grams    Toluene (%)                                                                              of IBB (%)                                ______________________________________                                        25      N       3.60     33.2       92.0                                      26      O       3.33     32.1       91.9                                      Comp. 10                                                                              P       3.39     11.0       92.3                                      Comp. 11                                                                              S       2.64     9.4        86.1                                      ______________________________________                                    

EXAMPLE 27

In a 300 ml autoclave equipped with a magnetic stirrer, Solid Base A(0.44 g) and p-diisoprpylbenzene (hereinafter referred to as "DIPB")(78.7 g) were charged under nitrogen, heated to 70° C. while stirring at1,000 rpm and reacted at the same temperature for 3 hours whilesupplying ethylene gas under pressure of 5 kg/cm² G.

After the reaction, the autoclave was cooled and the catalyst wasfiltered off. The reaction product was analyzed by gas chromatography tofind that it contained DIPB (0.1%), p-isopropyl-tert.-amylbenzene(17.8%) and p-di-tert.-butylbenzene (79.7%).

Preparation of Solid Base T

In the same manner as in the preparation of Solid Base A but addingpotassium hydroxide at 390° C., sintering the mixture of the alumina andpotassium hydroxide at 390° C. and using metal sodium (1.25 g) in placeof metal potassium, Solid Base T was prepared.

EXAMPLE 28

In the same manner as in Example 1 but using Solid Base T (0.37 g) andcumene (80 g) and carrying out the reaction at 160° C. in a 200 mlautoclave, the alkylation was carried out. The conversion of cumene was46.4%, and the selectivity of TAB was 98.6%.

In Example 28, the catalyst was still active at the end of the reactionand the alkylation could be further carried out by using the samecatalyst.

What is claimed is:
 1. A process for preparing an alkyl-substituted hydrocarbon comprising alkylating an aromatic hydrocarbon having at least one hydrogen atom at an alpha-position in a side chain with an olefin in the presence of a solid base as a catalyst, wherein said solid base is one which is obtainable by reacting an alumina containing 1.3 to 15% by weight of water and an alkali metal in an inert gas atmosphere at a temperature of 200° to 600° C.
 2. The process according to claim 1, wherein the aromatic hydrocarbon having the hydrogen atom at the alpha-position in the side chain has 1 to 10 carbon atoms in the side chain.
 3. The process according to claim 2, wherein the aromatic hydrocarbon is at least one selected from the group consisting of toluene, ethylbenzene, isopropylbenzene and diisopropylbenzene.
 4. The process according to claim 1, wherein the olefin has 2 to 20 carbon atoms.
 5. The process according to claim 4, wherein the olefin is selected from the group consisting of ethylene and propylene.
 6. The process according to claim 1, wherein the alkylation temperature is from 20° to 200° C.
 7. The process according to claim 1, wherein the reaction of the water-containing alumina and the alkali metal is carried out at a temperature of 250° to 550° C.
 8. The process according to claim 1, wherein the reaction of the water-containing alumina and the alkali metal is carried out at a temperature of 260° to 480° C.
 9. The process according to claim 1, wherein the alkali metal is at least one selected from the group consisting of sodium and potassium.
 10. The process according to claim 9, wherein the alkali metal is potassium.
 11. The process according to claim 1, wherein the amount of the alkali metal is 1.01 to 2 times the molar equivalent of water contained in the alumina.
 12. The process according to claim 11, wherein the water content in the alumina is from 1.3 to 15% by weight.
 13. The process according to claim 12, wherein the water content in the alumina is from 2 to 10% by weight.
 14. The process according to claim 13, wherein the aromatic hydrocarbon is at least one selected from the group consisting of toluene, ethylbenzene, isopropylbenzene and diisopropylbenzene.
 15. The process according to claim 1, wherein the alkali metal is sodium and said solid base is obtainable by reacting the sodium and alumina in an inert gas at atmosphere at a temperature of 200° to 390° C. 